Insecticidal esters of 1-acenaphthenol

ABSTRACT

Cyclopropanecarboxylic acid esters of 1-acenaphthenol and substituted 1-acenaphthenols possessing useful insecticidal properties.

United States Patent Crawford May 6, 1975 INSECTICIDAL ESTERS OFl-ACENAPHTHENOL [56] References Cited |75| Inventor: Robert .1.Crawford, Wyoming UNITED STATES PATENTS Ohm 3.641857 3mm Morgan i i260/468 [73] Assignee: The Procter & Gamble Company.

Cincinnati, Ohiu Primary Exuminer-lcromc D. (inldherg .Id M 97 AssistantE.\'amiuerA|lcn J. Robinson F] L ay I 4 Attorney. Agent. or FirmWil|iumKeith Turner; Jack [21 App]. No; 469,994 D SChzieffer; Richard C. WittcRelated US. Application Data S7 ABQTR CT I62] Division of Scr, No. l98434. Nov. I2. 197 I. Put. Nu. L I i A 3 .8405 84. Cyclopmpunccalrhuxylicacid esters ul l uccnuphthcnol and substituted l-nccnaphthenols pos-(521 U.S. Cl 424/305; 424/306 scssing useful insecticidal! pmpcrticm.(51] Int. Cl A. A0ln 9/24 2 Claim N Dr s (58] Field of Search 424/305.306; 260/468 H a INSECTICIDAL ESTERS OF l-ACENAPHTHENOL This is adivision. of application Ser. No. 198.434. filed Nov. l2. l97l. now U.S.Pat. No. 3.840.584 issued /8/74.

BACKGROUND OF THE INVENTION This invention relates to novelcyclopropanecarboxylic acid esters of l-acenaphthenol. and derivativesthereof. as well as insecticidal compositions containing said esters asan essential active ingredient.

Current trends in the chemical control of insects call for inherentlysafer materials which degrade very rapidly to non-toxic substances oncetheir purpose is ac complished. The safety of the widely usedchlorinated hydrocarbons. notably DDT. is currently under ques tionlargely because of their poor biodegradability and concomitantpersistence. Accordingly. there is a great demand for alternative broadspectrum insecticides which are suitable for the high volume usageentailed in agricultural applications. At the same time it is desirablefor new insecticides to exhibit a low order of toxic ity to warm-bloodedanimals. Of the several insecticidal classes which demonstrate lowmammalian toxicity and good biodegradability, it has long beenrecognized that pyrethrum. a naturallyoccurring insecticidal mixture.

possesses these desirable properties. In addition to the safetyadvantages, this natural mixture causes rapid knock-down and kill of abroad spectrum of insects; however. it is unstable to light. air. andheat. and is very expensive. The most active component of pyrethrum ispyrethrin I and a number of analogous compounds have been proposed forinsecticidal use. Allethrin. a typical synthetic pyrethrin-likeinsecticide. while more stable to light and heat than pyrethrum. isnevertheless expensive. a defect which is compounded by the fact thatthis substance is not appreciably synergized by the low cost synergizingagents such as piperonyl butoxide which are typically used ininsecticidal compositions. Because of instability. high cost and limitedsupply. the use ofpyrethrum and pyrethrin-like insecticides inagricultural applications has been precluded or seriously limited.

At the same time. it is well known that certain insects. in time. becomeimmune to the insecticidal properties of various chemical agents. To beefficient. an insecticide should be able to resist detoxification by theinsect. While biological mechanisms whereby insects are capable ofdetoxifying the various types of insecticidal compounds are not fullyunderstood. it is possible that. as with other biological systems.insects may in time develop new biochemical processes capable ofdetoxifying any particular insecticidal compound. In any event. it isdesirable to have included in the insecticidal armamentarium compoundswhich can be utilized once a given class ofinsects is found no longer torespond to conventional insecticidal compounds.

Many prior art insecticidal esters differ from one another and from thenatural pyrethrin l esters by virtue of synthetic modifications in thealcohol moiety of the ester. Other synthetic insecticides arepyrethrin-like esters modified in the acid portion of the estermolecule. For example. the copending application of Fanta. entitledlNSECTlClDAL ESTERS. Ser. No. 208,040, filed Dec. 9. 1971'. U.S. Pat.No. 3.679.667. July 25.

1972. to W. Puma; and U.S. Pat. No. 3.465.007. Sept.

2. 196). to M. Elliott. all relate to various synthetic insecticidalesters of the pyrethrum type. However. a

major shortcoming of the prior art synthetic pyrethrin l analogues istheir cost. and it is of major interest to provide a class of suchanalogues which is moderately priced. To achieve this. it is necessaryto provide a moderately priced alcohol which. when esterified with anappropriate cyclopropanecarboxylic acid. forms an insecticidal ester. lthas now been discovered that lacenaphthenol. and the various derivativesthereof. can be used in conjunction with cyclopropanecarboxylic acids toprovide insecticidal esters of the pyrethrum type at moderate cost.

It is therefore an object of this invention to provide novelinsecticidal l-acenaphthenol esters of cyclopropanecarboxylic acidswhich are biodegradable. el' fect rapid knock-down and kill of a broadspectrum of insects. possess low mammalian toxicity and are lesssusceptible to detoxification by insects than is pyrethrum. This andother objects are obtained by the present invention as will becomeapparent from the following disclosure.

SUMMARY OF THE INVENTION The novel compounds of the present inventioninclude certain cyclopropanecarboxylic acid esters of lacenaphthenol andsubstituted derivatives of lacenaphthenol.

This invention also encompasses insecticidal compo sitions comprising asan essential ingredient an insecticidal amount of certaineyclopropanecarboxylie acid esters of l-acenaphthenol or a substitutedlacenaphthenol.

As a method aspect. the present invention encompasses a method ofcombatting insects comprising applying an insecticidal amount of acyclopropanecarboxylic acid ester of l-acenaphthenol or substituted lacenaphthenol to an insect or insect habitat.

DETAILED DESCRIPTION OF THE INVENTION The cyclopropanecarboxylic acidesters of lacenaphthenol. tetrahydro-l-acenaphthenols and thederivatives thereof are of the formula 0 l R-C-OR wherein R is acyclopropanc moiety selected from the group consisting of (CH lf=CH and(CH c=cs wherein n is an integer of from 4 to 6. preferably 4. andwherein R is a l-acenaphthenyl or tetrahydro-lacenaphthenyl moiety ofthe formula 6 3 s 3 x I X wherein X, and X are each selected from thegroup ccnsisting of hydrogen, halogen. nitro. thiomethyl, al kyl. leg.ethyl, methyl. propyl, butyl, neopentyl, isopropyl,) alkoxyl, (cg,methoxyl, ethoxyl) sulfonyl methyl and the like. The substituents X andX; can be at any one or more of the positions marked 3, 4, 5. 6, 7 and 8on the above-indicated ring structures. The terification is at theiposition on the acenaphthenol or tetrahydro-l-acenaphthenol ringsystem.

The insecticidal compounds of this invention are prepared by esterifyingl-acenaphthenol, tetrahydro-lacenaphthenol. and substituted derivativesthereof, with cyclopropanecarboxylic acids or acid halides in the mannerhereinafter detailed. l-Acenaphthenol is prepared by the oxidation ofacenaphthene, an abundant constituent of coal tar (see L. Fieser and .l.Cason, J. Amer. Chem. Soc, 62, 432. i940). Substituted acenaphthenessuitable for use in the preparation of the substituted l-acenaphthenolsuseful in this invention can be prepared using standard syntheticprocedures. The substituted acenaphthenes can be oxidized to thecorresponding substituted i-accnaphthenols using the procedure of Fieserand Cason, above, and the result ing substituted Lacenaphthenols thenused to prepare the corresponding cyclopropanecarboxylic acid esters.The following exemplary substituted acenaphthene compounds. any of whichcan be converted to the corresponding substituted l-acenaphthenoisuseful herein, have been reported. along with others. in ChemicalAbstracts. Vols I-72, 3-chloroacenaphthene, 5- chloroacenaphthene,3,6dichloroacenaphthene, 5,6- dichloroacenaphthcne, S-bromoacenaphthene,3- tluoroacenaphthene, 4 fluoroacenaphthene. 5-fluoroo-nitroacenaphthene. 3iodoacenaphthene, 3- thiomcthylacenaphthene,3-nitroacenaphthene, 5- nitroacenaphthenc, 3,4-dinitroacenaphthene. 4-cthylacenaphthene. 4-methylacenaphthene, 4-tbutylacenaphthene.3-isopropylacenaphthene, 3.8- dimcthylacenaphthene,S-rnethoxyacenaphthene. 5- methoxy4-nitroacenaphthene.3,7di-tbutylacenaphthene, 5-propenylacenaphthene.

2a.3.4,5 Tetrahydrwi-acenaphthenol (and substituted derivatives thereof)can be prepared by the general procedure of Richter and Silver. J. Org.Chem. 33, 31K} (1968). Alternatively. these compounds (referred toherein simply as tetrahydrol accnaphthcnols") can be prepared bypartially hydrogenating the corresponding l-acenaphthenols. such asthose disclosed above, using well-known procedu es (eg, Pd/Chydrogenation).

The following l-acenaphthcnol and tetrahydro-l accnaphthenols arepreferred for use in the preparation of the compounds of this inventionby virtue of their low cost. case of preparation and the highinsecticidal activity of the cyciopropanecarboxylic esters which theyform. lacenaphthenol, 6-chloro- I acenaphthenol.fi-nitro-l-uccnaphthcnol, 5.b-dichlorol-acenaphthenol. S-methoxyl-acenaphthenol. tetrahydro-l-acenaphthenol and b-chloro-tetrahydroLacenaphthenol.

The cyciopropane carboxylic acids used to prepare the insecticidalesters of the instant invention can be prepared by standard proceduresdisclosed in the art. The copending application of Fanta. Ser. No.23,513, above, describes the preparation of 3-( 2,2- tetramethyleneethenyl)-2.2-dimethylcyclopropanecarboxylic acid; chrysanthemoylchloride can he prepared in the manner of Crombie. et al., J. Chem. Soc.3552 (i950); 2,2,3.3-tetramethylcyclopropanecarboxylic acid can beprepared in the manner of Matsui and Kitahara, Agr. Biol. Chem. (Tokyo)31, l l43 (1967) and converted to the acid chloride using thionylchloride.

The following gross synthetic scheme outlines the preparation of theinsecticidal esters of this invention:

(1} 0 lltcetic Pbs 4 Acid X X 1 2 2) NaOH then 0 ll X X R v C C1 0 ll RC 0 X Hcl wherein R, X and X are disclosed above.

According to the above outline, the esters of this invention areprepared by a step-wise process comprising: l) preparing thel-acenaphthenol, tetrahydro-lacenaphthenol, or derivatives thereofaccording to the procedures described in the foregoing references; (2)esterifying the alcohol with a stoichiometric amount of acyclopropanecarboxylic acid chloride which is also prepared by standardprocedures (above).

Alternatively, the esterification step of the present invention can beeffected in other ways. The lacenaphthenol. tetrahydrol -acenaphthenol,or deriva tives thereof as disclosed above, can be heated with theappropriate cyclopropanecarboxylie acid in the presence of a strong acid(e.g., H 50 HClO etc.) in an organic solvent capable of azeotropicallyboiling with water. thereby removing the water formed in theesterification. The l-acenaphthenol or tetrahydrod acenaphthenolcompound can also be heated with a lower alkyl ester of acyclopropanecarboxylic acid in the presence ofa basic catalyst such assodium hydroxide. potassium hydroxide. sodium alcoholate, or potassiumalcoholate. and the like. while continuously removing the lower alcoholformed through transesterification of the reaction system. In suchcases, the methyl, ethyl, n-propyl and isopropyl esters of the Cyclopropanecarboxylic acids are suitable. ln the most preferableesterification. the l-acenaphthenol, tetrahydro-l-acenaphthenol, orderivatives thereof. is allowed to react with a cyclopropanecarboxylicacid halide. preferably at temperatures from about C to about 100C. inan inert solvent. preferably in the presence of an agent such aspyridine. triethylamine or other suitable amine. such that theesterification proceeds with the formation of a hydrohalic acid saltwithin a short period of time. For this purpose. thecyclopropanecarboxylic acid chloride is the most preferred. although theacid bromide and the acid iodide can be employed.

The compounds of this invention can exist in several isomeric andoptically isomeric forms. e.g.. cisconfiguration. trans-configuration.dextroand levorotatory forms of each. etc.. and mixtures and racematesthereof. It is intended that the claims herein be construed to encompassall such forms and mixtures thereof. Preferred insecticidal estersherein are lacenaphthenol chrysanthemate. b-chloro-l acenaphthenolchrysanthemate. S-nitrol acenaphthenol chrysanthemate.tetrahydro-lacenaphthenol chrysanthemate. lacenaphthenol 2.2.-3.3-tetramethylcyclopropanecarboxylate. o-chloro-lacenaphthenol2.2.3.3-tetramethyleyclopropanecarboxylate, 5nitro-l-acenaphthenol2.2.3.3- tetramethylcyclopropanecarboxylate. tetrahydro-L acenaphthenol2.2.3.3-tetramethylcyclopropanecarboxylate. l-acenaphthenol3-(2.2-tetramethylene ethenyl)-2.Z-dimethylcyclopropanecarboxylate.b-chlorol-acenaphthenol 3-(2.2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylate. S-nitro-L acenaphthenol3-(2.2-tetramethylene cthenyl) 2.2- dimethylcyclopropanecarboxylate. andtetrahydro-lacenaphthenol 3-(2.2-tetramethylene ethenyl)-2.2-dimethylcyclopropanecarboxylate.

The preparation of the esters of the present invention is described inmore detail in the following examples. The inert organic solvents usedin the procedures are those which do not react with the l-acenaphthenolor tetrahydrol-acenaphthenol compound or with the cyclopropanecarboxylicacids or acid halides. Such solvents are preferably aprotic solventssuch as hexane, benzene. acetone. ether. glyme. and the like. Theexamples are not intended to be limiting. but only to demonstrate thepreparation of a variety of compounds of this invention.

EXAMPLE 1 lAcenaphthenol Chrysanthemate To an ice-cold. stirred solutionof 14.00 g. of (t)chrysanthemoyl chloride (cis-trans-isomer mixture) in100 ml. of anhydrous benzene, under static argon atmosphere, was addeddropwise 12.1 ml. of dry pyridine. The resulting mixture was cooled to5C. and 1 1.90 gv of solid l-acenaphthenol. prepared in the manner ofFieser and Cason. above, was added to the benzene solution in smallportions. This mixture was stirred for 2 hours at 0C. 20 hours at roomtemperature, and then was poured into 500 ml. of diethyl ether. Theether solution was washed with 100 ml. of 3M HCl. two 100 ml. portionsof 5% aqueous sodium carbonate. 100 ml. of saturated sodium chloridesolution. and dried over anhydrous magnesium sulfate. The ether wasremoved at reduced pressure on a rotary evaporator. The residue wasvacuum dried (C. 0.02 mm.) and afforded 22.99 g. of(i)cis-trans-l-acenaphthenol chrysanthemate whose structure was verifiedby spectral measurements.

In the above procedure. the l aeenaphthenol is replaced by an equivalentamount of the following substituted acenaphthenols. respectively:S-chloro-lacenaphthenol. 6-chloro-l-acenaphthenol. fibromo-lacenaphthenol. 6-fluorol -acenaphthenol. o-iodolacenaphthenol,S-nitro-l-acenaphthenol, 3-nitro-l acenaphthenol, 5.6-dichlorol=acenaphthenol. S methoxy-l-acenaphthenol. S-thiomethyl-lacenaphthenol,5-sulfonylmethyl-l-acenaphthenol. tetrahydro-l-acenaphthenol.3-ethyl-lacenaphthenol; the corresponding substituted l-acenaphthenoland tetrahydro-lacenaphthenol chrysanthemates are secured.

Using the apparatus and procedures of Example I. above.3-(2.2-tetramethylene ethenyl)-2.2-dimethylcy clopropanecarboxylic acidchloride and 2.23.3 tetramethyleyclopropanecarboxylic acid chloride.respectively. are reacted with the following alcohols: l acenaphthenol.o-chloro-l-acenaphthenol. S-nitro-l acenaphthenol. andtetrahydro-l-acenaphthenol and the following esters are secured:Lacenaphthenol 3- (2.2-tetramethylene ethenyl)Z.2dimethylcyclopropanecarboxylate. o-chlorol-acenaphthenol 3-(2.2-tetramethylene ethenyl)-2.2-dimethylcyclopropane carboxylate. S-nitrol-acenaphthcnol $12.2- tetramethyleneethenyl)-2,2dimethylcyclopropanecarboxylate. tetrahydro-l-acenaphthenol3- (2.2-tetramethylenc ethenylcyclopropanecarboxylate. l-acenaphthenol2.2.3.3-tetramethylcyclopropanecar boxylate. 6-chloro-1-acenaphthenol2.2.3.3 tetramethylcyclopropanecarboxylate. 5 -nitro-l acenaphthenol2.2.3.3-tetramethylcyclopropanecarboxylate andtetrahydro-l-acenaphthenol 2.2.3.3- tetramethylcyclopropanecarboxylate.

The following test is intended to illustrate the insecticidal propertiesof a representative ester herein. but is not intended to limit the scopeof the invention.

insecticidal Evaluation An insecticidal composition comprising the esterof (:)cis-trans'l-acenaphthenol chrysanthematc from Example I. dissolvedin acetone and dispersed in dis tilled water with Triton X-l00*emulsifier was prepared. The composition was applied for a ten secondperiod to houseflies retained in a 2 inches X 5 inches diameter screenedcage. The spray was applied from a Waters vertical spray tower operatingat 10 psi. and discharging about 30 ml. of material per minute throughan atomizer. The spray descends through an 8 inches stainless steelcylinder to test insects below the atomizer. The insects were retainedin the sprayed cages for mortality observations. Test compositionshaving the indicated percentage concentration of weight (W) of testcompound to spray volume (V) were utilized in the tests. The results areset forth in Table 1 below. lsooetyl phenyl polyethoxy ethanol ()PI:9-10 supplied by Rohm & Haas Company As can be seen from the foregoingdata. a representative compound of this invention possesses excellentinsecticidal properties. Additionally. the compounds of the instantinvention are substantially less toxic to mammals than are most commoninsecticides.

Similar results are secured when 5-chloro4- acenaphthenolchrysanthemate. 6chlorol acenaphthenol chrysanthcmate. 5,6-dichloro-lacenaphthenol chrysanthemate, 5-methoxyl acenaphthenol chrysanthemate.b-chlorotetrahydro-l acenaphthcnol chrysanthemate, 7-ethyl-tetrahydro-lacenaphthenol chrysanthemate. and 5-nitrolacenaphthenol chrysanthemate.respectively. are incorporated in the insecticidal composition in placeof the l-acenaphthenol chrysanthemate in the above test.

Using the general procedure described above. isomer mixtures ofl-acenaphthenol 3(2.2tetramethylene cthenyl)-2.Zdimethylcyclopropanecarboxylate, bchlorol -acenaphthenol 3-(ZJ-tetramethylene ethenyl)2.l-dimethylcyclopropane carboxylatc. Snitro-lacenaphthenol 3-(2.2-tetramethylenc ethenyl)-2.2-dimcthylcyclopropanecarboxylate. tetrahydrol acenaphthenol 3 2 .Z tetramethylene ethcnylcyclopropanecarboxylate. l-acenaphthenol 2.2.3.3-tetramethylcyclopropanecarboxylate. o-chloro l acenaphthenol 2.2.3.3tetramethylcyclopropanecar boxylate, S-nitro-l-aeenaphthenol 2.2.3.3-tetramethylcyclopropanecarboxylate and tetrahydro-L accnaphthenol2.2.3.3-tetramethylcyclopropanecarboxylate. respectively, are applied tohouseflies. to Southern army worm. the Mexican bean beetle. the peaaphid, the adult mosquito. adult stable flies. black carpet beetlelarva. webbing clothes moth larva. adult rice weevils. and adultsawtooth grain beetles and these insects are controlled. As can be seen.the compounds herein are effective against a wide variety of insects.

Insecticidal compositions containing the esters of the present inventioncan be formulated and utilized as oil solutions. emulsifiableconcentrates, wettahle powders. dusts. aerosols, or impregnated intowood. fabrics, etc., and provide a long lasting residual effect. Suchcompositions can include the generally employed carriers or diluents andauxiliary agents which are well-known to those skilled in the art. Forexample. suitable dusts can be prepared by admixing the compounds of theinvention with dry free-flowing powders such as clay. ben tonite,fullers earth. diatornaceous earth. pyrophyllite. attapulgite. calciumcarbonate. chalk or the like. The acti\e compounds of the inventionnormally comprise up to about HI /l by weight of such dust formulations.An amount of up to about 3'71 is preferred and is suitable for mostapplications.

Likewise. suspensions or dispersions of the com pounds in a non-solvent.such as water. can be suitably employed for the treatment of foliage.Also suitably employed are solutions of the insecticides of thisinvention in oil which is emulsified in water. Examples of oil solventsinclude hydrocarbons such as benzene and tol uenc. halogenatedhydrocarbons such as chloroben zene. chloroform. fluorotrichlorornethaneand di chloro-dilluoromethane. and commercial mixtures of hydrocarbonssuch as the common Stoddard solvent. petroleum ethcrs. and the like.

Aerosols can be prepared by dissolving the compounds of the invention ina highly volatile liquid carrier such as trifluorochloromethane.nitromethane. di-

chlorodifluorocthane and the like, or by dissolving such compounds in aless volatile soivent. such as benzene or kerosene. and admixing theresulting solution with a highly volatile liquid aerosol carrier such asthe polyfluorohydrocarbons commonly used as aerosol propellants.

The insecticidal esters of this invention are useful for destroying avariety of insects. Accordingly. a method aspect of the presentinvention comprises combating insects by applying to said insects. or toan insect habi tat. one or more of novel compounds disclosed herein.

Preferably the esters of this invention are employed in combination witha synergistic agent, for example, piperonyl butoxide, piperonylsulfoxide, B-butoxyJT- thiocyanodiethyl ether and the like.

What is claimed is:

l. A process for combatting insects comprising applying to said insects.or to their habitat. an insecticidally effective amount of acyclopropanecarboxylic acid ester of the formula wherein R is acyclopropane moiety selected from the group consisting of c11 e3 5 c csI (CH3)2C-CH and H 0, en

wherein n is an integer of from 4 to 6 and wherein R is al-acenaphthenyl or tetrahydro-l-acenaphthenyl moiety of the formulawherein X, and X are each selected from the group consisting ofhydrogen. halogen. nitro, thiomethyl. straight or branched chain alkylcontaining from about I to 5 carbon atoms. alkoxyl containing from aboutl to 2 carbon atoms and sulfonylmethyl.

2. The process according to claim 1 wherein the cyclopropanecarboxylicacid ester is a member selected from the group consisting ofl-acenaphthenol chrysanthemate. o-chloro-l-acenaphthenol chrysanthemate.-initro l-acenaphthenol chrysanthemate, tetrahydrol-acenaphthenolchrysanthemate, l-acenaphthenol 2.-2.3.3-tetramethylcyclopropanecarboxylate. 6-chl0ro l-acenaphthenol2,2,3,3-tetramethylcyclopropanecar' boxylate. S-nitrol-acenaphthenol2.2.3.3- tetra methylcyclopropanecarboxylate. tetrahydrol acenaphthenol2.2.3.3-tetramethylcyclopropanecarboxylate, lacenaphthenol3-(2,2.tetramethylene eth

1. A PROCESS FOR COMBATTING INSECTS COMPRISING APPLYING TO SAID INSECTS,OR TO THEIR HABITAT, AN INSECTICIDALLY EFFECTIVE AMOUNT OF ACYCLOPROPANECARBOXYLIC ACID ESTER OF THE FORMULA
 2. The processaccording to claim 1 wherein the cyclopropanecarboxylic acid ester is amember selected from the group consisting of 1-acenaphthenolchrysanthemate, 6-chloro-1-acenaphthenol chrysanthemate,5-nitro-1-acenaphthenol chrysanthemate, tetrahydro-1-acenaphthenolchrysanthemate, 1-acenaphthenol2,2,3,3-tetramethylcyclopropanecarboxylate, 6-chloro-1-acenaphthenol2,2,3,3-tetramethylcyclopropanecarboxylate, 5-nitro-1-acenaphthenol 2,2,3,3-tetramethylcyclopropanecarboxylate, tetrahydro-1-acenaphthenol2,2,3,3-tetramethylcyclopropanecarboxylate, 1-acenaphthenol3-(2,2,-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylate,6-chloro-1-acenaphthenol 3-(2,2-tetramethyleneethenyl)-2,2-dimethylcyclopropanecarboxylate, 5-nitro-1-acenaphthenol3-(2,2-tetramethylene ethenyl)-2,2-dimethylcyclopropanecarboxylate, andtetrahydro-1-acenaphthenol 3-(2,2-tetramethyleneethenyl)-2,2-dimethylcyclopropanecarboxylate.